organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

5-(2-Methyl-5-nitro­phen­yl)-1H-tetra­zole

aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
*Correspondence e-mail: fudavid88@yahoo.com.cn

(Received 9 September 2008; accepted 11 September 2008; online 17 September 2008)

In the title compound, C8H7N5O2, the benzene ring makes a dihedral angle of 45.7 (2)° with the tetra­zole ring. In the crystal structure, the mol­ecules are linked into a chain running along the a axis by N—H⋯N hydrogen bonds, and the chains are linked through ππ inter­actions between the tetra­zole rings [centroid–centroid distance = 3.450 (2) Å].

Related literature

For the use of tetra­zole derivatives in coordination chemisty, see: Arp et al. (2000[Arp, H. P. H., Decken, A., Passmore, J. & Wood, D. J. (2000). Inorg. Chem. 39, 1840-1848.]); Dai & Fu (2008[Dai, W. & Fu, D.-W. (2008). Acta Cryst. E64, o1445.]); Wang et al. (2005[Wang, X.-S., Tang, Y.-Z., Huang, X.-F., Qu, Z.-R., Che, C.-M., Chan, C. W. H. & Xiong, R.-G. (2005). Inorg. Chem. 44, 5278-5285.]); Xiong et al. (2002[Xiong, R.-G., Xue, X., Zhao, H., You, X.-Z., Abrahams, B. F. & Xue, Z.-L. (2002). Angew. Chem. Int. Ed. 41, 3800-3803.]).

[Scheme 1]

Experimental

Crystal data
  • C8H7N5O2

  • Mr = 205.19

  • Monoclinic, P 21 /c

  • a = 4.9057 (10) Å

  • b = 16.938 (3) Å

  • c = 11.463 (2) Å

  • β = 98.65 (3)°

  • V = 941.7 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.11 mm−1

  • T = 298 (2) K

  • 0.25 × 0.18 × 0.15 mm

Data collection
  • Rigaku Mercury2 diffractometer

  • Absorption correction: multi-scan (CrystalClear, Rigaku, 2005[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.971, Tmax = 0.977

  • 9281 measured reflections

  • 2085 independent reflections

  • 1434 reflections with I > 2σ(I)

  • Rint = 0.056

Refinement
  • R[F2 > 2σ(F2)] = 0.082

  • wR(F2) = 0.203

  • S = 1.13

  • 2085 reflections

  • 137 parameters

  • H-atom parameters constrained

  • Δρmax = 0.30 e Å−3

  • Δρmin = −0.29 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯N4i 0.86 1.98 2.775 (4) 154
Symmetry code: (i) x+1, y, z.

Data collection: CrystalClear (Rigaku, 2005[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

Tetrazole derivatives have found wide range of applications in coordination chemistry because of their multiple coordination modes as ligands to metal ions and for the construction of novel metal-organic frameworks (Wang et al., 2005; Xiong et al., 2002). We report here the crystal structure of the title compound, 5-(2-methyl-5-nitrophenyl)-1H-tetrazole, (Fig.1).

The benzene ring makes a dihedral angle of 45.7 (2)° with the tetrazole ring owing to the C–C bond bridge which force the two rings to be twisted from each other. The bond distances and angles of the tetrazole rings are in the usual ranges (Wang et al., 2005; Arp et al., 2000; Dai & Fu, 2008).

The crystal packing is stabilized by N—H···N hydrogen bonds (Table 1), which link the molecules into chains running parallel to the a axis (Fig. 2). The adjacent chains are linked through ππ interactions between the tetrazole rings [centroid–centroid distance = 3.450 (2) Å] of the molecules at (x, y, z) and (1-x, 1-y, 1-z).

Related literature top

For the use of tetrazole derivatives in coordination chemisty, see: Arp et al. (2000); Dai & Fu (2008); Wang et al. (2005); Xiong et al. (2002).

Experimental top

Under nitrogen protection, 2-methyl-5-nitrobenzonitrile (30 mmol), NaN3 (45 mmol) and NH4Cl (33 mmol) were added in a flask and then DMF (50 ml) was added. The mixture was stirred at 383 K for 20 h, the resulting solution was poured into ice water (100 ml) and then hydrochloric acid (6 mol/l) was added to control the pH value to 6. The white solid obtained was filtered and washed with distilled water. The crude product was recrystallized with ethanol to obtain colourless block-shaped crystals of the title compound.

Refinement top

All H atoms were positioned geometrically and treated as riding with C—H = 0.93 Å (aromatic), 0.96 Å (methyl) and N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(C,N) and Uiso(H) = 1.5Ueq(Cmethyl).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. Part of the crystal packing of the title compound, showing a hydrogen- bonded (dashed lines) chain running along the a axis. H atoms not involved in hydrogen bonding have been omitted for clarity.
5-(2-Methyl-5-nitrophenyl)-1H-tetrazole top
Crystal data top
C8H7N5O2F(000) = 424
Mr = 205.19Dx = 1.447 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1775 reflections
a = 4.9057 (10) Åθ = 2.4–27.1°
b = 16.938 (3) ŵ = 0.11 mm1
c = 11.463 (2) ÅT = 298 K
β = 98.65 (3)°Block, colourless
V = 941.7 (3) Å30.25 × 0.18 × 0.15 mm
Z = 4
Data collection top
Rigaku Mercury2
diffractometer
2085 independent reflections
Radiation source: fine-focus sealed tube1434 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.056
Detector resolution: 13.6612 pixels mm-1θmax = 27.2°, θmin = 3.0°
ω scansh = 66
Absorption correction: multi-scan
(CrystalClear, Rigaku, 2005)
k = 2121
Tmin = 0.971, Tmax = 0.977l = 1414
9281 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.082Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.203H-atom parameters constrained
S = 1.13 w = 1/[σ2(Fo2) + (0.0655P)2 + 0.9796P]
where P = (Fo2 + 2Fc2)/3
2085 reflections(Δ/σ)max = 0.001
137 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
C8H7N5O2V = 941.7 (3) Å3
Mr = 205.19Z = 4
Monoclinic, P21/cMo Kα radiation
a = 4.9057 (10) ŵ = 0.11 mm1
b = 16.938 (3) ÅT = 298 K
c = 11.463 (2) Å0.25 × 0.18 × 0.15 mm
β = 98.65 (3)°
Data collection top
Rigaku Mercury2
diffractometer
2085 independent reflections
Absorption correction: multi-scan
(CrystalClear, Rigaku, 2005)
1434 reflections with I > 2σ(I)
Tmin = 0.971, Tmax = 0.977Rint = 0.056
9281 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0820 restraints
wR(F2) = 0.203H-atom parameters constrained
S = 1.13Δρmax = 0.30 e Å3
2085 reflectionsΔρmin = 0.29 e Å3
137 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.0317 (10)0.86679 (19)0.3611 (3)0.1152 (15)
O20.2052 (8)0.7689 (2)0.4436 (3)0.0930 (12)
N10.5142 (5)0.48416 (16)0.3549 (2)0.0425 (7)
H10.67660.49700.34190.051*
N40.0825 (5)0.48791 (16)0.3638 (2)0.0416 (7)
N30.1836 (6)0.41763 (16)0.4075 (3)0.0473 (7)
C10.2904 (6)0.52855 (17)0.3320 (3)0.0360 (7)
N20.4451 (6)0.41548 (16)0.4018 (3)0.0470 (7)
C20.2681 (6)0.61097 (19)0.2897 (3)0.0397 (7)
C70.3890 (7)0.6358 (2)0.1932 (3)0.0485 (9)
C30.1193 (7)0.6641 (2)0.3495 (3)0.0426 (8)
H30.03490.64730.41250.051*
C40.1007 (7)0.7403 (2)0.3140 (3)0.0506 (9)
C60.3672 (8)0.7152 (2)0.1624 (3)0.0565 (10)
H60.45100.73330.09990.068*
N50.0555 (8)0.7961 (2)0.3775 (3)0.0676 (10)
C50.2254 (9)0.7676 (2)0.2220 (4)0.0628 (11)
H50.21360.82060.20060.075*
C80.5334 (9)0.5794 (2)0.1215 (4)0.0628 (11)
H8A0.41640.53470.09920.094*
H8B0.70200.56180.16770.094*
H8C0.57380.60560.05190.094*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.197 (4)0.0494 (19)0.105 (3)0.033 (2)0.042 (3)0.0013 (19)
O20.107 (3)0.089 (2)0.095 (3)0.032 (2)0.054 (2)0.003 (2)
N10.0275 (13)0.0435 (15)0.0576 (18)0.0007 (12)0.0105 (12)0.0030 (13)
N40.0317 (13)0.0391 (14)0.0558 (17)0.0045 (11)0.0129 (12)0.0006 (13)
N30.0422 (16)0.0397 (15)0.0616 (19)0.0060 (13)0.0132 (14)0.0008 (14)
C10.0293 (15)0.0369 (16)0.0428 (17)0.0034 (13)0.0090 (13)0.0002 (14)
N20.0434 (16)0.0359 (14)0.0637 (19)0.0033 (12)0.0144 (14)0.0005 (13)
C20.0305 (15)0.0437 (17)0.0455 (18)0.0033 (13)0.0076 (13)0.0006 (15)
C70.0400 (18)0.061 (2)0.0447 (19)0.0012 (16)0.0085 (15)0.0040 (17)
C30.0394 (17)0.0451 (18)0.0443 (19)0.0003 (14)0.0096 (14)0.0048 (15)
C40.051 (2)0.049 (2)0.052 (2)0.0093 (16)0.0103 (17)0.0000 (17)
C60.061 (2)0.055 (2)0.057 (2)0.0009 (19)0.0216 (19)0.0211 (19)
N50.086 (3)0.055 (2)0.062 (2)0.0235 (19)0.013 (2)0.0028 (18)
C50.070 (3)0.050 (2)0.071 (3)0.008 (2)0.019 (2)0.016 (2)
C80.067 (3)0.072 (3)0.056 (2)0.012 (2)0.029 (2)0.000 (2)
Geometric parameters (Å, º) top
O1—N51.220 (5)C7—C81.505 (5)
O2—N51.222 (5)C3—C41.352 (5)
N1—C11.324 (4)C3—H30.93
N1—N21.346 (4)C4—C51.377 (5)
N1—H10.86C4—N51.477 (5)
N4—C11.326 (4)C6—C51.371 (5)
N4—N31.357 (4)C6—H60.93
N3—N21.294 (4)C5—H50.93
C1—C21.477 (4)C8—H8A0.96
C2—C71.396 (5)C8—H8B0.96
C2—C31.401 (4)C8—H8C0.96
C7—C61.391 (5)
C1—N1—N2108.6 (2)C3—C4—C5122.2 (3)
C1—N1—H1125.7C3—C4—N5118.7 (3)
N2—N1—H1125.7C5—C4—N5119.1 (3)
C1—N4—N3107.7 (2)C5—C6—C7121.7 (3)
N2—N3—N4108.4 (2)C5—C6—H6119.2
N1—C1—N4107.5 (3)C7—C6—H6119.2
N1—C1—C2128.3 (3)O1—N5—O2123.2 (4)
N4—C1—C2124.0 (3)O1—N5—C4118.9 (4)
N3—N2—N1107.9 (3)O2—N5—C4117.9 (3)
C7—C2—C3120.6 (3)C6—C5—C4118.8 (4)
C7—C2—C1121.7 (3)C6—C5—H5120.6
C3—C2—C1117.7 (3)C4—C5—H5120.6
C6—C7—C2117.8 (3)C7—C8—H8A109.5
C6—C7—C8120.0 (3)C7—C8—H8B109.5
C2—C7—C8122.2 (3)H8A—C8—H8B109.5
C4—C3—C2118.9 (3)C7—C8—H8C109.5
C4—C3—H3120.6H8A—C8—H8C109.5
C2—C3—H3120.6H8B—C8—H8C109.5
C1—N4—N3—N20.4 (4)C1—C2—C7—C84.1 (5)
N2—N1—C1—N40.3 (4)C7—C2—C3—C41.6 (5)
N2—N1—C1—C2174.4 (3)C1—C2—C3—C4178.6 (3)
N3—N4—C1—N10.4 (4)C2—C3—C4—C50.7 (6)
N3—N4—C1—C2174.5 (3)C2—C3—C4—N5179.8 (3)
N4—N3—N2—N10.2 (4)C2—C7—C6—C51.9 (6)
C1—N1—N2—N30.1 (4)C8—C7—C6—C5176.7 (4)
N1—C1—C2—C749.1 (5)C3—C4—N5—O1166.6 (4)
N4—C1—C2—C7137.0 (3)C5—C4—N5—O112.5 (6)
N1—C1—C2—C3131.2 (3)C3—C4—N5—O214.0 (6)
N4—C1—C2—C342.7 (5)C5—C4—N5—O2166.9 (4)
C3—C2—C7—C62.9 (5)C7—C6—C5—C40.4 (6)
C1—C2—C7—C6177.4 (3)C3—C4—C5—C61.7 (6)
C3—C2—C7—C8175.7 (3)N5—C4—C5—C6179.2 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N4i0.861.982.775 (4)154
Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC8H7N5O2
Mr205.19
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)4.9057 (10), 16.938 (3), 11.463 (2)
β (°) 98.65 (3)
V3)941.7 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.25 × 0.18 × 0.15
Data collection
DiffractometerRigaku Mercury2
diffractometer
Absorption correctionMulti-scan
(CrystalClear, Rigaku, 2005)
Tmin, Tmax0.971, 0.977
No. of measured, independent and
observed [I > 2σ(I)] reflections
9281, 2085, 1434
Rint0.056
(sin θ/λ)max1)0.642
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.082, 0.203, 1.13
No. of reflections2085
No. of parameters137
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.30, 0.29

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N4i0.861.982.775 (4)154
Symmetry code: (i) x+1, y, z.
 

Acknowledgements

This work was supported by a start-up grant from Southeast University to Professor Ren-Gen Xiong.

References

First citationArp, H. P. H., Decken, A., Passmore, J. & Wood, D. J. (2000). Inorg. Chem. 39, 1840–1848.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationDai, W. & Fu, D.-W. (2008). Acta Cryst. E64, o1445.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationRigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWang, X.-S., Tang, Y.-Z., Huang, X.-F., Qu, Z.-R., Che, C.-M., Chan, C. W. H. & Xiong, R.-G. (2005). Inorg. Chem. 44, 5278–5285.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationXiong, R.-G., Xue, X., Zhao, H., You, X.-Z., Abrahams, B. F. & Xue, Z.-L. (2002). Angew. Chem. Int. Ed. 41, 3800–3803.  Web of Science CrossRef CAS Google Scholar

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ISSN: 2056-9890
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